Hexahydro-1 3 5-tris-(4-hydroxyaryl)-s-triazines

ABSTRACT

NOVEL HEXAHYDRO-1,3,5-TRI-(4-HYDROXYARYL)-S-TRIAZINES HAVE BEEN PREPARED. THESE COMPOUNDS ARE EFFECTIVE STABILIZERS FOR ORGANIC MATERIALS, SUCH AS A-OLEFIN POLYMERS AND COPOLYMERS, ACETAL POLYMERS, POLYAMIDES, POLYESTERS AND POLYURETHANES, AGAINST THE DELETERIOUS EFFECTS OF OXYGEN, HEAT AND LIGHT.

United States Patent O 3,639,336 HEXAHYDRO-l,3,5-TRIS-(4-HYDROXYARYL)-s-TRIAZINES Warren L. Beears, Brecksville, Ohio, assignor to The B. F.Goodrich Company, New York, NY.

No Drawing. Original application Oct. 31, 1968, Ser. No. 772,363, nowPatent No. 3,567,724, dated Mar. 2, 1971. Divided and this applicationMar. 18, 1970, Ser. No. 14,860

Int. Cl. C081? 45/60; C08g 51/60; C10m 1/36 US. Cl. 26045.8 N 13 ClaimsABSTRACT OF THE DISCLOSURE NovelheX'ahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines have been prepared.These compounds are effective stabilizers for organic materials, such asa-ole-fin polymers and copolymers, acetal polymers, polyamides,polyesters and polyurethanes, against the deleterious elfects of oxygen,heat and light.

Patented Feb. 1, 1972 cent to it in the 3 and ring positions. Thepresent compounds consist of a symmetrical hexahydro-1,3,5-triazinenucleus containing three hindered phenolic moieties attached throughcarbonyl linkages. The heXahydro-1,3,5- tris-(4-hydroxyaryl)-s-triazinesare effective stabilizers for 5 organic materials which are subject tooxidative, thermal or photochemical degradation. They possess lowvolatility, are nonstaining, and are extremely elfective protectiveagents for organic polymeric materials, both natural and synthetic. Thecompounds of this invention are especial- 1y useful as stabilizers fora-monoolefin homopolymers and copolymers particularly polyethylene,polypropylene and ethylene-propylene copolymers and terpolymer,polyacetal homopolymers and copolymers, polyamides, polyesters andpolyurethanes.

DETAILED DESCRIPTION The compounds of the present invention arerepresented by the structural formula This is a division of applicationSer. No. 772,363 filed Oct. 31, 1968, now US. Pat. No. 3,567,724.

BACKGROUND OF THE INVENTION The ability of the hindered phenoliccompounds to stabilize materials against oxidative degradation is widelyrecognized. More recently, the trend has been to prepare wherein R and Rare tertiary alkyl groups containing from 4 to 18 carbon atoms, R, ishydrogen or alkyl groups containing from 1 to 18 carbon atoms, R, ishydrogen or an alkyl group containing from 1 to 4 carbon atoms, and m isan integer from 2 to 5.

Preferred compounds of the present invention will have the formulaSUMMARY OF THE INVENTION I have now prepared novel hexahydro 1,3,5tris-(4- hydroxyaryDs-triazine compounds having a hydroxyl grouphindered by two alkyl radicals immediately adjawherein R is hydrogen ora methyl group and n is an integer between 4 to 12. These compounds areexcellent stabilizers for organic materials which are subject tooxidative, thermal and photochemical degradation. It is notable with thehexahydro-1,3,5-tris-(4-hydroxyaryl)-striazines of the present inventionthat although they are high molecular weight materials, the weight ratioof the phenol to the total weight of the molecule remains high.Accordingly, effective stabilization of organic materials with lowlevels of the hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines ispossible. This results in a significant economic advantage to the user.The present compounds are also effective stabilizers for hightemperature applications due to their extremely low volatility.

Hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines within the scope of thepresent invention include:

hexahydro-1,3,5-tris-}3-( 3,5,-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine,

hexahydro-1,3,5 -tris-p- 3,5 -di-t-amyl-4-hydroxyphenyl)propionyl-s-triazine,

hexahydro-1,3,5-tris-fi-(3-t-butyl-5-t-amyl-4-hydroxyphenyl)propionyl-s-triazine,

hexahydro-1,3,5-tris-/3- 3,5-di 1-methyl-1-ethylpropyl)-4-hydroxyphenyl]propionyl-s-triazine,

hexahydro-1,3,5-tris-p-[3,5-di( 1,1,2,2-tetramethylpropyl)4-hydroxyphenyl] propionyl-s-triazine,

hexahydro-1,3,5-tris-fl- 3,5-di 1,1-dimethylpeutyl)-4- hydroxyphenyl]propionyl-s-triazine,

hexahydro- 1,3,5-tris-fi- [3,5 -di-( 1,1-dimethyldecyl)-4-hydroxyphenyl] propionyl-s-triazine,

hexahydro-l,3,5-tris-1S- 3,5-di-t-butyl-4-hydroxyphenyl)a-methylpropionyl-s-triazine,

hexahydro-1,3,5-tris-fi-( 3,5 -di-t-amyl-4-hydroxyphenyl)a-methylpropionyl-s-triazine,

hexahydro-l,3,5-tris-fl-( 3,5 -di-t-butyl-4-hydroxyphenyl)butenyl-s-triazine,

hexahydro-1,3,5-tris-'y-(3,5-di-t-butyl-4-hydroxyphenyl)butenyl-s-triazine and the like.

It is not necessary that the phenolic substituents on thehexahydro-s-triazine ring be identical. Unsymmetricalhexahydro-s-triazines, that is, substituted with dissimilar hinderedphenolic substituents, may be prepared and are within the scope of thepresent invention.

, The novel hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines are highmelting crystalline solids soluble in acetone, methylethyl ketone,diethyl ether, dioxane, tetrahydrofuran, chloroform and aromatichydrocarbons such as benzene and toluene. They are slightly soluble inaliphatic hydrocarbons and alcohols such as methanol and ethanol.Recrystallization of these compounds is best achieved from hotchloroform or a mixture of hot chloroform and hexane. Generally, thecompounds will range in color from white to a very pale yellow whenpure. The presence of solvent residues or other impurities willgenerally cause yellowing of the compounds upon standing, especiallyupon exposure to air.

The hexahydro 1,3,5tris-fi-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine is a whitecrystalline solid existing in three metastable states, anrat-crystalline form, a fl-crystalline form and a glass. The temperatureand recrystallization medium employed generally determine whichcrystalline form is obtained. The a-crystalline form is obtained uponrecrystallization from chloroform solution. The B-form can be obtainedupon recrystallizing from boiling toluene. Mixtures of the aand B-formgenerally will result if the compounds are precipitated fromN,N-dimethylformamide by the addition of water. Both the aandfi-crystalline forms melt at 233 C. to 235 C. Initial melting in therange of 80 to 105 C. will be observed with the u-form, however, this isactually the transition to the fl-crystalline form.

The hexahydro 1,3,5 tris- (4-hydroxyary1) -s-triazines are prepared bycombining three mols of the appropriate hindered phenol with one mol ofa hexthydro-s-triazine of the formula wherein R is hydrogen or an alkylgroup containing 1 to 4 carbon atoms. A metal salt of the hinderedphenol, formed by the action of a base on the phenol, is reacted withthe above-depicted hexahydro-s-triazine compound. The process forpreparing the metal salt of the phenol is fully set forth in U.S. Patent2,974,171. Elevated temperatures (SO-150 C.) and inert diluents, such asN,N-dimethylformamide, are generally employed to form thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines.

The hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines of this inventionare extremely useful stabilizers. They are useful in a wide variety oforganic materials to prevent oxidative, thermal or photochemicaldegradation. Their ability to efiectively stabilize organic materials isattributed, at least partially, to the ability of thehexahydro-s-triazine ring to be substituted 'with three hindered phenolgroups, thus providing a high molecular weight compound without undulydiluting the hindered hydroxyl grouping.

Organic materials which are stabilized in accordance with the presentinvention include both natural and synthetic polymers. The hexahydro1,3,5 tris-(4-hydroxyaryl)-s-triazines are advantageously employed forthe stabilization of homopolymers of ethylene, propylene, 'butene-l,isobutylene, pentene-l, heXene-l, 4-methylpentene-1, and the like, orcopolymers thereof such as et-hylene-propyl ene coplymer,ethylene-butene-l copolymer, 4-methyl-1- pentene-hexene-l copolymer andthe like; ethylene-propylene-diene rubbers wherein the diene is1,4-hexadiene, 2- methyl-1,4-hexadiene, dimethyl-1,4,9-decatrienes,dicyclopentadiene, vinylcyclohexene, vinyl norborene, ethylidenenorbornene, methylene norbornene, norboradiene, methyl norbornadiene,methyl tetrahydroindene and the like; polyacetal resins, such 'as acetalhomopolymers derived from the polymerization of formaldehyde or acetalcopolymers derived from trioxane; polyesters obtained by thecondensation of saturated or unsaturated anhydrides or dibasic acids,such as maleic, furmaric, itaconic or terephathalic an hydrides orfumaric, adipic, azelaic, sebacic or isophthalic acids, with a glycolsuch as propylene glycol, ethylene glycol, diethylene glycol, neopentylglycol or trimethyl pentanediol; polyetheror polyester-derivedpolyurethanes; and polyamides such as polycaprolactam or those obtainedby the condensation of hexamethylenediamine with adipic or sebacic acidor the like. The present compounds are also useful stabilizers fornatural rub- =ber; halogenated rubber; conjugated diene polymers such aspolybutadiene, copolymers of butadiene with styrene, acrylonitrile,acrylic acid, alkyl acrylates or methacrylates, methylvinyl ketone,.vinyl pyridine and the like, polyisoprene or polychloroprene; vinylpolymers such as polyvinyl chloride, polyvinyl fluoride, polyvinylidenechloride, polyvinyl acetate, copolymers of vinyl chloride withvinylidene chloride, butadiene, styrene vinyl esters, ,3- olefinicallyunsaturated acids and esters thereof, ,5- olefinically unsaturatedketones and aldehydes and the like; homopolymers and copolymers ofacrylic monomers such as acrylic acid, methacrylic acid, methylacrylate, methyl methacrylate, ethyl acrylate, 2-ethylhexyl acrylate,acrylamide, methacrylamide, N -methylol acrylamide, acrylonitrile,methacrylonitrile or the like; polycarbonates; epoxy resins such asthose obtained by the condensation of epichlorohydrin with bisphenols;epichlorohydrinethylene oxide or propylene oxide copolymers; and thelike.

'In addition to the above-mentioned polymeric organic materials thehexahydro-l,3,5-tris-(4-hydroxyaryD-s-tri- 'azines may also be employedto stabilize organic nonpolymeric materials. Such materials includewaxes, syntheticand petroleum-derived lubricating oils and greases;mineral oils such as fat, tallo, lard, codliver oil and sperm oil;vegetable oils such as castor, linseed, peanut, palm, cottonseed or thelike; fuel oil; diesel oil; gasoline; and the like.

The hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines are especiallyuseful stabilizers for u-monoolefins, homopolymers and copolymers,polyacetal homopolymers and copolymers, polyamides, polyesters andpolyurethanes. High and low density polyethylene, polypropylene,polyisobutylene and poly(4-methyl-1-pentene) have markedly improvedresistance of oxidative, thermal and photochemical degradation whenstabilizing amounts of the present compounds are incorporated therein.Ethylene-propylene copolymers and ethylene-propylene terpolymerscontaining less than about 10% by weight of a multiple unsaturated thirdmonomer are also elfectively stabilized with the hexahydro 1,3,5tris-(4-hydroxyaryl)-s-triazines. Polymer blends, that is, physicalmixtures of two or more a-monoolefin copolymers or homopolymers are alsostabilized in accordance with the present invention.

The amount of stabilizer employed will vary with the particular materialto be stabilized and also the particularhexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine employed. Generally,however, for effective stabilization of most organic materials an amountof the hexahydro-1,3,5 tris (4 hydroxyaryl)-s-triazine ranging fromabout 0.001% to about 10% of weight based on the weight of the organicmaterial will be employed, In most applications the amount of stabilizeremployed will vary between about 0.01% and about 5% by weight. With thepoly(a-monoolefin) homopolymers and copolymers, about 0.01 to about 1.5%by weight of the hexahydro-1,3,5-tris- (4-hydroxyaryl)-s-triazine basedon the weight of the polymer will be employed. Certain of thehexahydro-1,3,5-tris- (4-hydroxyaryl)-s-triazines will be more useful ingiven applications then others. This is attributable, at least in part,to the compatibility of the particular hexahydro-1,3,5-tris-(4-hydroxyaryl)-striazine with the organic material to bestabilized as a result of varying the alkyl substituents and theirposition on the phenol ring or varying the number of methylene unitslinking the phenolic moiety to the triazine nucleus.

The compounds of this invention are readily incorporated into mostorganic materials and generally require no special processing.Conventional methods of incorporation have generally been found to beadequate. For example, the hexahydro-1,3,5-tris-(4hydroxyaryl)-s-triazines are incorporated into polymers by mixing on arubber mill or in a Banbury mixer; or they may be added alone, in asuitable solvent, or masterbatched with other ingredients to a solutionor dispersion of the polymer. The solubility of the present compounds ina wide variety of organic solvents facilitates their use in solution andalso renders them compatible with most oils and lubricants.

The hexahydro-l,3,5-tris-(4-hydroxyaryl)-s-triazines are compatible withconventional compounding ingredients such as processing oils,plasticizers lubricants, antisticking agents, fillers, reinforcingagents, sulfur and other curing agents, accelerators, anti-foamingagents, rust inhibitors and the like. They are also compatible withother known antoxidants, antiozonants, color and heat stabilizers,ultraviolet absorbers and the like and when employed in combination withcertain of these stabilizers a synergistic effect will be produced.Synergism results, for example, when thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines are combined withperoxide decomposing compounds such as dithiocarbamates, zincdialkylthiophosphates or organic sulfides such as those described in US.Pat. 2,519,755. An especially marked synergistic efiect is obtained whenthe compounds of the present invention are combined with diesters ofB-thiodipropionic acid having the formula ROOCCH CH SCH CH COOR whereinR is an alkyl group containing from 6 to 20 carbon atoms such as octyl,decyl lauryl, cetyl, stearyl, palmityl, benzyl, cyclohexyl and the like.Typically, the amount S-dialkylthiodipropionate employed will be variedbetween about 1 part and 5 parts per par-t of thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine in order to achieveoptimum synergistic activity. Other useful stabilizer compositionspossessing synergistic activity are obtained when the hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazines are combined with other phenoliccompounds, which are well known to the art, such as2,6-di-t-butyl-4-methylphenol, tetra[methylene-3-(3,5-di-t-butyl-4hydroxyphenyl)propionate]methane,1,3,5trimethyl-2,4,6-tris-(3,5-di-t-butyl-4-hydroxybenzyl)benzene,octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate,tris-(3,5-di-t-butyl 4 hydroxyphenyl)phosphate, 4,4thiobis-(3-methyl-6-t-butylphenol) and the like.

The following examples illustrates the invention more fully. In theseexamples all parts and percentages are given on a weight basis unlessotherwise indicated.

Example I A glass reactor equipped with a stirrer, condenser anddropping funnel was charged with 21.6 grams (0.4 mol) powdered sodiummethoxide and 785 grams of N,N-dimethylformamide which had beenpreviously dried and distilled over calcium hydride. To this suspensionwas added 453.2 grams (2.2 mols) of redistilled 2,6-di-t-butylphenol andthe resulting reaction mixture heated with stirring and under a nitrogenblanket to distill oif methanol. The distillation was terminated whenthe distillate temperature reached 149 C. The reaction mixture was thenallowed to cool to room temperature and 116 grams (0.666 mol)1,3,S-triacryl-perhydro-s-triazine dissolved in 785 grams ofN,N-dimethylforrnamide containing about 2 grams of2,6-di-t-butyl-p-cresol added. The resulting reaction mixture was thenheated at 135 C. for 3 hours maintaining the nitrogen blanket. grams of1:1 hydrochloric acid was then charged to the cooled reaction mixture.The sodium chloride formed was removed from the reaction mixture byfiltration and 10.9 grams of sodium hydrosulfite added to the resultingfiltrate. The N,N- dimethylformamide was then partially removed undervacuum and the resulting mass heated to approximately 80 C. and 154grams of distilled water added with rapid stirring. This mixture wasallowed to cool to 20 C. with continuous stirring. The resulting creamcolored solid was collected by filtration and washed successively with10% aqueous ethanol and 70% aqueous ethanol. The white crystalline solidobtained upon recrystallization from chloroform-hexane melted at 237-239C. on a melting block. A sample nine times recrystallized fromchloroform-hexane had a melting point, determined in a capillary, of228229 C. (uncorrected). Elemental analysis of this product agreed withthe calculated values for hexahydro-l,3,5-tris-fi-(3,5-di-t-butyl-4hydr0xyphenyl)propionyl-s-tn'azine. Analysis of the compound by infraredand nuclear magnetic resonance spectroscopy confirmed the compound to behexahydro-1,3,5-tris-p3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine. Hexahydro-1,3,5-trisfl- 3,5-di-t-amyl-4-hydroxyphenyl) propionyl-s-triazine was also prepared usingthe above-described procedure.

Example II A polymer blend of 75 parts polyvinyl chloride having adensity of 1.56 and 25 parts of a methyl methacrylatebutadiene-styrenepolymer compounded with three parts of a tin stabilizer, 5 partstitanium dioxide and 0.5 part of a lubricant was milled 4 minutes at 390F. and then aged in a 400 F. forced-air oven. After aging for about 30to 40 minutes, significant color change was noted in the abovecomposition. After 50 to 60 minutes copious amounts of HCl was evolved.When 1 part hexahydro 1,3,5tris-13-(3,5di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine, as preparedin Example I, was incorporated as additional stabilizer and the sampletested under identical test conditions, significant color change of thesample did not develop until after minutes. Similarly, no gas evolutionwas apparent even after minutes aging.

Example III A conventional high density polyethylene stabilized with 0.1part hexahydro-l,3,5-tris- 3-(3,5di-t-butyl-4-hydroxyphenyl)propionyl-s-triazine was compared withpolyethylene stabilized with several commercially available stabilizersand an unstabilized control. The recipes employed in these runs are setforth in Table I with test results. The samples were tested for oxygenabsorption at C.

TABLE I Samnle 1 2 3 4 High density polyethylene 100 100 100 100Hexahydro-1,3,5-tris-fl-(3,5-di-t-butyl-4- hydroxy phenyl) -s-triazine0. 1 1,3,5-trimethyl-2,4,6-tris-(3,5-di-t-butyl- 4-hydroxybenzyl)henzene 0. l Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate- 0.1 Induction time (hours) 0.5 135 110 80 The additives wereincorporated into the polyethylene by dissolving them in acetone,suspending the polyethylene therein, and then removing the acetone undervacuum. The stabilized polyethylene was hot milled (290300 F.) for 5minutes, sheeted ofl, placed in a 4-cavity ACS mold shimmed to thedesired thickness and heated at 300 F. for minutes, the last 5 minutesof which 150 tons pressure was applied. The samples were cooled whilemaintaining this pressure.

The oxygen absorption was determined on 10 mil molded samples which werepressed on aluminum screens and aged in pure oxygen at 140 C. in amodified Scott tester block. The induction period, that is, the timerequired for autooxidation of the polyethylene to occur, was recorded.

Similar improved stabilities were achieved when hexahydro 1,3,5tris;3-(3,5 di-t-amyl-4-hydroxyphenyl) propionyl-s-triazine wasincorporated in polyethylene.

Example IV Hexahydro-1,3,5-tris-fl-(3,5 di-t-butyl 4hydroxyphenyl)propionyl-s-triazine was incorporated in polypropylene byitself and in combination with fl-dialkylthio- Parts Ingredient Sample14 Sample 15 Natural rubber 100 100 Zinc oxide 85 85 Titanium dioxid 1515 Ultramarine bin 0. 2 0. 2 Stearie acid"... 2.0 2.0

Sulf 3 3 Benzothiazyl disulfide 1. 0 1. 0Hexahydro-1,3,5-tris-B-(3,5-di-t-butyl-4- 1. 0

hydroxyphenyl)propionyl-s-triazine The samples were cured at 284 F. forthe time required to develop optimum cure (as determined with aviscurometer) These samples were then aged for 72 hours in oxygen bombsmaintained at C. Physical properties (unaged and aged) for the controland stabilized samples are set forth in Table IV.

One hundred parts ethylene-propylene terpolymer (53% ethylene, 43%propylene, 4% ethylidene norbormm) was masterbatched with parts PEFblack and 25 parts naphthenic oil and compounded as follows:

Example V To demonstrate the ability of thehexahyd'ro-1,3,5-trisfl-(3,S-di-t-butyl-4-hydroxyphenyl)-s-triazine tostabilize polypropylene against the deleterious elfects of ultravioletlight, samples 5-8 and 11-13 of Example IV were exposed in a Xenondry-cycle weatherometer maintained at -100 C. The samples were rotatedto insure identical exposure for all samples and observed at regularintervals. Results of this test are set forth in Table HI.

A natural rubber white stock was prepared in accordance with thefollowing recipe:

dipropionates in the same manner as employed in Ex- Ingredients: Partsample III. The recipes are set forth below in Table II. Masterbatch 200Samples were prepared by molding the stabilized p0ly- 35 Zinc oxide 5mer at 400 F. and 4000 p.s.i. for two minutes. The Stearic acid 1.0samples were then transferred to a cold press maintained Sulfur 1.5 at4000 p.s.i. for a two minute cooling period. 25 milMercaptobenzothiazole 1.5 samples were aged in an air-circulating ovenat C. Tetramethylthiuram disulfide 0.8 The polypropylene samples weredeemed to have failed Dipentamethylene thiuram tetrasulfide 0.8 at thefirst signs of crazing. Test results are also tabu- Hexahydro 1,3,5tris-B-(3,5-di-t-butyl-4-hylated in Table II.droxyphenyl)propionyl-s-triazine 1.0

TABLE II Sample 5 6 7 8 9 10 11 12 13 Polypropylene 100 100 100 100 100100 100 100 100Partshexahydro-1,3,5tris-fl-(3,b-di-t-butyll-hydroxyphenyl)-s-triazine0.1 0.25 0.5 0.25 0.5 0.1 0.25 0.5 Parts B-dilaurylthiodipropionate 0.2 1. 0 Parts fl-distearylth iodipropionate 0. 25 0. 25 0. 25 Hours tocrazing 1 960 1,500 1,728 2,322 3,498 1, 720 2,148 2, 232

Samples were air aged at and tensile properties of the rubber determinedat 7 day intervals. The stability of the polymer is evident from thetabulation of the test results in Table V.

TABLE v Aging time (days) 0 7 14 2 1FiiSiJiJiiiiiif-fii?-Rii'?33:12::.ELFII- it? 3% 92 Example VIII ExampleIX The following compositions were stabilized with varying 9 amounts ofhexahydro-1,3,5-tris-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazineas follows:

10 Example XII Several foam samples were stabilized with hexahydro-Sample Material 253% 1,3,5tris-13-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s- 16 ABS min 0. 5 5triazine and aged at 25 C. in an air atmosphere contain- {l jjj jj 32,582? 3;? ing 100 parts per million nitrogen dioxide. The foam com- 19Plus acrylonilrile copolymer positions are set forth in Table VII. Theywere conven- ZQ fiyggg gne tionally cured and the compression modulusdetermined. 35:33:31: iilifiiyifi tiiit rtraurism33:3:::::::::::: it?Percent change the mmpressw 24 Polyoxymethylene 0,5 in Table VIIrepresents a measure of the softening 25 Metal copolymer resin 5 orhardening of the foams during aging.

TABLE v11 Sample 2s 29 30 31 32 33 34 35 36 37 3s 3 Foam composition:

Natural rubber Polybutadiene rubber Styrene-butadiene rubber Polystyrene(parts) Feldspar Hexahydro-1,3,5-tris-fi-(3,5di-t-butyl-4-hydroxyphenyl)propionyl-s-trizaine (parts) -5 Original compression modulus (grams/in?)250 250 Percent change compression modulus after 72 hours-.. +111 +15. 4

(parts) All of the compositions (lo-25) set forth above had improvedoxidative stability over the unstabilized materials.

Example X An ethyl acrylate-acrylonitrile (70%/30%) stabilized I claim:

1. A stabilized composition of matter which comprises an organicmaterial and from about 0.001% to about 10% by weight of ahexahydro-1,3,5-(4-hydroxyaryD-s-triazine of the formula wherein R and Rare tertiary alkyl groups containing from 4 to 18 carbon atoms, R is aradical selected from the group consisting of hydrogen or alkylcontaining from 1 to 18 carbon atoms, R is a radical selected from thegroup consisting of hydrogen or alkyl containing from 1 to 4 carbonatoms and m is an integer from 2 to 5.

2. The stabilized composition of matter of claim 1 wherein thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine has the formula ExampleXI One parthexahydro-1,3,5-tris-fi-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-s-triazinewas employed to stabilize an elastomeric polyurethane (Estane 5740Xl40)containing 0.5 part of a commercially available stabilizer (Tinuvin P).This sample (26) and an unstabilized control (sample 27) were air-agedfor one week at 120 C. Test results are tabulated in Table VI.

wherein R is a radical selected from the group consisting of hydrogen ormethyl.

3. The stabilized composition of matter of claim 2 wherein the organicmaterial is selected from the group consisting of rat-monoolefinhomopolymers, tX-IIIOIIOOlCfiIl copolymers, acetal homopolymers, acetalcopolymers, polyamides having recurring amide groups as integral partsof the main polymer chain, polyesters and polyurethanes.

4. The stabilized composition of matter of claim 2 wherein R and R ofthe hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine are tertiary alkylgroups containing from 4 to 12 carbon atoms, R is hydrogen and theorganic material is selected from the group consisting of umonoolefinhomopolymers, a monoolefin copolymers, acetal homopolyrners, acetalcopolymers, polyamides hav- 11 ing recurring amide groups as integralparts of the main polymer chain, polyesters and polyurethanes.

5. The stabilized composition of matter of claim 4 wherein thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine is employed in amountbetween about 0.01 to about 5% by weight and ishexahydro-1,3,5-tris-j3-(3,5-di-tbutyl-4-hydroxyphenyl)propionyl-s-triazine.

6. The stabilized composition of matter of claim 4 wherein thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazinc is employed in amountbetween about 0.01% to about 5% by weight and ishexahydro-1,3,S-tris-B-(3,5-di-t-an1yl-4-hydroxyphenyl)propionyl-s-triazine.

7. The stabilized composition of matter of claim 4 wherein thehexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine is employed'in amountbetween about 0.01% to about Ra 1'11 i Fla- )mo IHQE Fin- R e T Q Ra R:R:

wherein R and R are tertiary alkyl groups containing from 4 to 18 carbonatoms, R is a radical selected from the group consisting of hydrogen oralkyl containing from 1 to 18 carbon atoms, R is a radical selected fromthe group consisting of hydrogen or alkyl containing from 1 to 4 carbonatoms and m is an integer from 2 to 5; and (c) from about 1 part toabout 5 parts per part of the hexahydro-1,3,5-tris-(4-hydroxyaryl)-s-triazine of a compound selected from the group consisting of aphenolic antioxidant and p-dialkylthiodipropionate of the formula ROOCCHCH S--CH CH COOR wherein R is an alkyl group containing from 6 to 20car-hon atoms.

10. The stabilized composition of matter of claim 9 wherein thehexahydro-1,3,5-tris-(4-hydroXyary1)-s-triazine has the formula R3 R3 R3wherein R and R are tertiary alkyl groups containing from 4 to 12 carbonatoms, R is hydrogen and R is a radical selected from the groupconsisting of hydrogen or methyl.

11. The stabilized composition of matter of claim 10 wherein thefi-dialkylthiodipropionate is fl-dilaurylthiodipropionate orfl-distearylthiodipropionate.

12. The stabilized composition of matter of claim 11 wherein thea-monoolefin polymer is polyethylene.

13. The stabilized composition of matter of claim 11 wherein thea-monoolefin polymer is polypropylene.

References Cited UNITED STATES PATENTS 3,282,939 11/1966 Spivack et a1260247.7 3,53 0,127 9/ 1970 Biland 260-248 3,531,483 9/1970 Gilles260248 3 ,5 67,724 3 1971 Beears 260248 3,584,047 6/1971 Dexter et al.260559 DONALD E. CZAJA, Primary Examiner R. A. WHITE, Assistant ExaminerUS. Cl. X.R.

7 3 3? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3 ,639,336 Dated February 1972 lnventor( Warren L. Beears It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 10 lines &9-59, Claim 2, the formula should read C-CH-CH OH R 3 2R R: R 0 H CH 0 R4 'R R F n I I I HO CH -CH-C--N N-- H-CH OH t CH I. YR2 3 3 2 Signed and sealed this 20th day of February 1973.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. ROBERT GOTTSCHALK Commissioner of PatentsAttesting Officer

